CN1687323A - Method for producing liquid biological energy sources by using monosaccharide, oligosaccharide and sugar alcohol - Google Patents
Method for producing liquid biological energy sources by using monosaccharide, oligosaccharide and sugar alcohol Download PDFInfo
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- CN1687323A CN1687323A CN 200510033827 CN200510033827A CN1687323A CN 1687323 A CN1687323 A CN 1687323A CN 200510033827 CN200510033827 CN 200510033827 CN 200510033827 A CN200510033827 A CN 200510033827A CN 1687323 A CN1687323 A CN 1687323A
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Abstract
The present invention relates to a method for producing liquid biological energy source by utilizing monosaccharide, oligose and its alditol. Said method includes the following steps: A. using monosaccharide, oligose and its alditol as raw material, adding methyl alcohol and dehydration agent and concentrated sulfuric acid to make reflux reaction to make saccharides be etherified; B. distilling at 70-75 deg.C, collecting condensate; or adding dried calcium hydroxide to remove concentrated sulfuric acid, filtering and collecting filtrate, the above-mentioned obtained condensate or filtrate is the etherified biological energy source.
Description
Technical field
The invention belongs to the bioenergy field, relate to a kind of method of producing liquid biological energy source, especially relate to a kind of method of utilizing monose, oligose and sugar alcohol thereof to produce liquid biological energy source.
Background technology
Carbohydrate is renewable resource the abundantest on the earth.In today of energy growing tension, exploitation is that the bioenergy alternative ore energy of raw material seems very urgent with the carbohydrate.The main method of utilizing carbohydrate to produce bioenergy at present is to adopt fermentative Production alcohol, but also there are some defectives in the zymamsis method.The one, fermented substrate there is strict demand, can not utilize the fiber polysaccharide; The 2nd, to expend a large amount of sugar in the fermenting process to keep yeast growth, cause the wasting of resources; The 3rd, the distillation power consumption is bigger.Therefore, adopting carbohydrate fermentation to produce alcohol does not also generally promote because of the cost problem as bioenergy.
Though the physics fuel value of carbohydrate has only 1/3 of gasoline, tellurian plant produces hundreds billion of tons of carbohydrate by photosynthesis every year, as long as it 1% is changed into the energy, then can satisfy the needs of present human being's production and domestic energy.The restriction carbohydrate is that burning is insufficient as the principal element of the energy, and its major cause is that itself exists with solid-state form, and they form caramel earlier during burning, have stoped its further burning.If can adopt method of modifying to make carbohydrate become liquid at normal temperatures, its point of ignition is significantly reduced, then can address the above problem, facilitate carbohydrate to replace diesel oil or gasoline.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing monose, oligose and sugar alcohol thereof to produce liquid biological energy source, to hang down molecule carbohydrate such as monose and oligose and sugar alcohol thereof is raw material, itself and methyl alcohol reaction are formed sugar ether (methyl ether of sugar), product is in a liquid state at normal temperatures, obtain boiling point, point of ignition is suitable with methyl alcohol, fuel value and firepower are greater than the liquid biological energy source of methyl alcohol, this energy is the boiling point and point of ignition is low, fuel value the is high new bio energy, is expected to part even all replaces gasoline or diesel oil commonly used at present.
For reaching above-mentioned purpose, the method for utilizing monose, oligose and sugar alcohol thereof to produce liquid biological energy source of the present invention may further comprise the steps:
A. be raw material with monose, oligose and sugar alcohol thereof, add methyl alcohol and dewatering agent and the vitriol oil and carry out back flow reaction, make the carbohydrate etherificate;
B. 70～75 ℃ of distillations, collect phlegma; Perhaps add exsiccant calcium hydroxide and remove the vitriol oil, filter, collect filtrate;
Above-mentioned phlegma that obtains or filtrate are the bioenergy of etherificate, are that a kind of boiling point, point of ignition and methyl alcohol are suitable, and fuel value and firepower are greater than the liquid biological energy source of methyl alcohol.
Monose can be aldose or the ketose that contains 3～8 carbon atoms, as glucose, pectinose, wood sugar etc.; The one-component that oligose can be made up of 2～12 monose of the same race or not of the same race and the carbohydrate of blending ingredients are as maltose, sucrose, maltodextrin etc.; Sugar alcohol be above-mentioned monose and oligose after hydrogenation, obtain product, as N.F,USP MANNITOL, maltose alcohol etc.
The purpose of adding dewatering agent is to absorb the water molecules that discharges in the etherification reaction process, and the carbohydrate etherification reaction is carried out fully.Therefore, dewatering agent can be silica gel, molecular sieve, anhydrous sodium sulphate etc. do not form complex compound and polymkeric substance with methyl alcohol, carbohydrate a reagent.The vitriol oil is both as dewatering agent, again as catalyzer.
The adding proportion of described carbohydrate and methyl alcohol is by quality: volume is 1: 4～8.
The temperature of reaction of described back flow reaction is 75～150 ℃, and the reaction times is 1～5 hour.
Principle of the present invention is: sugar or sugar alcohol molecule make it to be powder or crystal state owing to contain great amount of hydroxy group thereby form hydrogen bond between the molecule.After with its hydroxyl methyl-etherified, no longer form hydrogen bond between the glycan molecule, thereby form low, the incendive etherificate product of boiling point.
Beneficial effect of the present invention is: the raw material sources of the liquid biological energy source that (1) is used to produce are extensive, and preparation process need not high temperature, high pressure, and the reaction times is short, and environmental pollution is few.(2) the present invention has successfully obtained to be in a liquid state at normal temperatures, boiling point, point of ignition and methyl alcohol are suitable, fuel value and firepower are greater than the liquid biological energy source of methyl alcohol, this energy is the boiling point and point of ignition is low, fuel value the is high new bio energy, is expected to part even all replaces gasoline or diesel oil commonly used at present.
Description of drawings
Fig. 1 is the fuel combustion determinator;
Fig. 2 is a water temperature variation diagram in the process combustion.
Embodiment
Embodiment one:
At normal temperatures, in the reactor by 1: 4: 3～5: 0.1～0.3 (quality: volume: quality: quality) add glucose, methyl alcohol, dry silica gel and the vitriol oil, 100 ℃ of following back flow reaction 3 hours, cooling.Add 3 times of exsiccant calcium hydroxides to the sulfuric acid quality and remove sulfuric acid (the new water that forms is absorbed by silica gel), filter, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.Washed silica gel utilizes after the drying again.
Adopt distillation method to increase energy consumption, but can remove remaining glucose.
Embodiment two:
At normal temperatures, in the reactor by 1: 5: 2～4: 0.1～0.2 (quality: volume: quality: quality) add wood sugar, methyl alcohol, anhydrous sodium sulphate and the vitriol oil, 100 ℃ of following back flow reaction 2 hours, cooling.Add 3 times of exsiccant calcium hydroxides and remove sulfuric acid to the sulfuric acid quality.Remove by filter sodium sulfate, filtrate is the bioenergy of etherificate; Also can go out product at 70～75 ℃ of straight run distillation.
Adopt distillation method to increase energy consumption, but can remove remaining wood sugar.
Embodiment three:
At normal temperatures, in the reactor by 1: 6: 3～6: 0.2～0.4 (quality: volume: quality: quality) add pectinose, methyl alcohol, molecular sieve and the vitriol oil, 100 ℃ of following back flow reaction 1 hour, cooling.Add 3 times of exsiccant calcium hydroxides and remove sulfuric acid to the sulfuric acid quality.Filter, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.
Adopt distillation method to increase energy consumption, but can remove remaining pectinose.
Embodiment four:
At normal temperatures, in the reactor by 1: 7: 2～4: 0.1～0.5 (quality: volume: quality: quality) add maltose, methyl alcohol, silica gel and the vitriol oil, 120 ℃ of following back flow reaction 5 hours, cooling.Add 3 times of exsiccant calcium hydroxides and remove sulfuric acid (the new water that forms is absorbed by silica gel) to the sulfuric acid quality.Remove by filter silica gel, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.Washed silica gel utilizes after the drying again.
Adopt distillation method to increase energy consumption, but can remove remaining maltose.
Embodiment five:
At normal temperatures, in the reactor by 1: 8: 3～5: 0.1～0.5 (quality: volume: quality: quality) add sucrose, methyl alcohol, silica gel and the vitriol oil, 130 ℃ of following back flow reaction 5 hours, cooling.Add 3 times of exsiccant calcium hydroxides to the sulfuric acid quality and remove sulfuric acid (the new water that forms is absorbed by silica gel), filter, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.
Adopt distillation method to increase energy consumption, but can remove remaining sucrose.
Embodiment six:
At normal temperatures, in the reactor by 1: 6: 3～5: 0.2～0.3 (quality: volume: quality: quality) add maltodextrin, methyl alcohol, dry silica gel and the vitriol oil, 150 ℃ of following back flow reaction 5 hours, cooling.Add 3 times of exsiccant calcium hydroxides to the sulfuric acid quality and remove sulfuric acid, remove by filter silica gel, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.Washed silica gel utilizes after the drying again.
Adopt distillation method to increase energy consumption, but can remove remaining maltodextrin.
Embodiment seven:
At normal temperatures, in the reactor by 1: 7: 4～6: 0.3～0.5 (quality: volume: quality: quality) add N.F,USP MANNITOL, methyl alcohol, anhydrous sodium sulphate and the vitriol oil, 75 ℃ of following back flow reaction 4 hours, cooling.Add 3 times of exsiccant calcium hydroxides to the sulfuric acid quality and remove sulfuric acid, filter, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.
Adopt distillation method to increase energy consumption, but can remove remaining N.F,USP MANNITOL.
Embodiment eight:
At normal temperatures, in the reactor by 1: 8: 3～6: 0.2～0.4 (quality: volume: quality: quality) add maltose alcohol, methyl alcohol, molecular sieve and the vitriol oil, 85 ℃ of following back flow reaction 4 hours, cooling.Add 3 times of exsiccant calcium hydroxides to the sulfuric acid quality and remove sulfuric acid, filter, filtrate is the bioenergy of etherificate; Also adding calcium hydroxide not goes out product at 70～75 ℃ of straight run distillation.
Adopt distillation method to increase energy consumption, but can remove remaining maltose alcohol.Glucose and methyl alcohol reaction with embodiment one are example, and the effect of estimating products therefrom of the present invention is as follows:
1. adopt the reaction of glucose and methyl alcohol, the product of acquisition is liquid, and density and methyl alcohol are approaching.
10.0g glucose+80ml methyl alcohol+30g dry silica gel+1.0g vitriol oil, back flow reaction under differing temps distills out product, obtains column data (table 1) down:
The reaction of glucose and methyl alcohol obtains the performance of etherificate product under table 1. different condition
| Unreacted glucose (g) | Density (g/ml) | Carbon residue (%) | Boiling point (℃) | |
| 100 ℃, 130 ℃ of 3h, 150 ℃ of 1h, 1h methyl alcohol | ?0.56 ?1.20 ?0.83 ?- | ?0.83 ?0.83 ?0.83 ?0.78 | ?0.02 ?0.02 ?0.02 ?0 | ????64 ????64 ????64 ????62 |
2. the product firepower of Huo Deing is better than methyl alcohol
In order to measure the vigor of glucose methyl ether, the present invention has designed following experiment.On iron stand, install at a distance of 2 on the iron hoop of 6cm, above iron hoop place 1 in the culture dish that fills 40ml water, diameter 6cm, hang 1 in thermometer; Following iron hoop is put 1 in the culture dish (as Fig. 1) that fills 5ml methyl alcohol or glucose methyl ether, diameter 6cm.Iron stand is placed in the big wooden case that keeps out the wind at the four sides.
Light the fuel in the following culture dish, from the be filled with water temperature of culture dish of igniting opening entry different time, the water temperature lift velocity is seen Fig. 2.
As seen from Figure 2, when adopting glucose ether to make fuel, the water temperature lift velocity is apparently higher than methyl alcohol, and the vigor that glucose ether is described is greater than methyl alcohol.
3. flame height
The methyl alcohol and the glucose methyl ether that take by weighing 5.0g respectively are in the culture dish of 6cm in diameter, and the highest flame height is measured in ignition.The result shows that the former is 12.3cm, and the latter is 15.9cm, exceeds 29.2%.
Claims (6)
1, utilize monose, oligose and sugar alcohol thereof to produce the method for liquid biological energy source, it is characterized in that, may further comprise the steps:
A. be raw material with monose, oligose and sugar alcohol thereof, add methyl alcohol and dewatering agent and the vitriol oil and carry out back flow reaction, make the carbohydrate etherificate;
B. 70～75 ℃ of distillations, collect phlegma; Perhaps add exsiccant calcium hydroxide and remove the vitriol oil, filter, collect filtrate;
Above-mentioned phlegma that obtains or filtrate are the bioenergy of etherificate, are that a kind of boiling point, point of ignition and methyl alcohol are suitable, and fuel value and firepower are greater than the liquid biological energy source of methyl alcohol.
2, method according to claim 1 is characterized in that: described monose is aldose or the ketose that contains 3～8 carbon atoms.
3, method according to claim 1 is characterized in that: the described oligose one-component that monose of the same race or not of the same race is formed by 2～12 and the carbohydrate of blending ingredients.
4, method according to claim 1 is characterized in that: described dewatering agent is selected from silica gel, molecular sieve, anhydrous sodium sulphate.
5, method according to claim 1 is characterized in that: the adding proportion of described carbohydrate and methyl alcohol is by quality: volume is 1: 4～8.
6, method according to claim 1 is characterized in that: the temperature of reaction of described back flow reaction is 75～150 ℃, and the reaction times is 1～5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510033827 CN1284845C (en) | 2005-03-31 | 2005-03-31 | Method for producing liquid biological energy sources by using monosaccharide, oligosaccharide and sugar alcohol |
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|---|---|---|---|
| CN 200510033827 CN1284845C (en) | 2005-03-31 | 2005-03-31 | Method for producing liquid biological energy sources by using monosaccharide, oligosaccharide and sugar alcohol |
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| CN1687323A true CN1687323A (en) | 2005-10-26 |
| CN1284845C CN1284845C (en) | 2006-11-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870715A (en) * | 2010-06-08 | 2010-10-27 | 暨南大学 | Ether energy and preparation method and application thereof |
| CN111718390A (en) * | 2020-07-28 | 2020-09-29 | 福建省格兰尼生物工程股份有限公司 | Sterol cold separation formula liquid and application thereof |
-
2005
- 2005-03-31 CN CN 200510033827 patent/CN1284845C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870715A (en) * | 2010-06-08 | 2010-10-27 | 暨南大学 | Ether energy and preparation method and application thereof |
| CN101870715B (en) * | 2010-06-08 | 2012-09-05 | 暨南大学 | Ether energy and preparation method and application thereof |
| CN111718390A (en) * | 2020-07-28 | 2020-09-29 | 福建省格兰尼生物工程股份有限公司 | Sterol cold separation formula liquid and application thereof |
| CN111718390B (en) * | 2020-07-28 | 2023-06-16 | 福建省格兰尼生物工程股份有限公司 | Sterol cold precipitation formula liquid and application thereof |
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| CN1284845C (en) | 2006-11-15 |
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Granted publication date: 20061115 |